Fungicidal alkoximinomethyldioxazine derivatives

ABSTRACT

The invention relates to alkoximinomethyldioxazine compounds and intermediates thereof, and to process for the preparation of the alkoximinomethyldioxazine compounds and intermediates thereof. The alkoximinomethyldioxazine compounds have the structure:

The invention relates to novel alkoximinomethyldioxazine derivatives, toa process for their preparation and to their use as fungicides, and alsoto novel intermediates and to a plurality of processes for theirpreparation.

It is already known that certain alkoximinomethyldioxazine derivativesof a constitution similar to those described below have fungicidalproperties (compare, for example, WO-A 9504728). However, the fungicidalactivity of these compounds, in particular at low application rates,leaves something to be desired. The novel alkoximinomethyldioxazinederivatives of the general formula (I) have now been found

in which

G represents a single bond, alkanediyl which is optionally interruptedby heteroatoms (but where the carbon atom to which R¹ is attached isalways linked to a carbon atom of the alkanediyl chain) or a grouping

 in which

R³ represents in each case optionally substituted alkyl or cycloalkyl,

R¹ represents hydrogen, cyano or in each case optionally substitutedalkyl or cycloalkyl,

R² represents hydrogen or in each case optionally substituted alkyl orcycloalkyl,

Z represents in each case optionally substituted alkyl, alkenyl,alkinyl, cycloalkyl, cycloalkenyl, aryl or heterocyclyl and

E¹, E², E³ and E⁴ are identical or different and, independently of oneanother, each represents hydrogen, alkyl, halogenoalkyl or hydroxyalkyl,or

E¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring and

L¹, L², L³ and L⁴, are identical or different and, independently of oneanother, each represents hydrogen, halogen, cyano, nitro, in each caseoptionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinylor alkylsulphonyl.

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, alkanediyl, alkenyl or Alkinyl, are in each casestraight-chain or branched, including in combination with heteroatoms,such as in alkoxy, alkylthio or alkylamino. If an alkyl or alkanediylchain is interrupted by more than one heteroatom, these can be identicalor different. If an alkyl or alkanediyl chain is interrupted by morethan one oxygen atom, two oxygen atoms are not directly adjacent.

Halogen generally represents fluorine, chlorine, bromine or iodine, andalso pseudohalogens, such as, for example, cyano, preferably fluorine,chlorine, bromine or cyano, in particular fluorine or chlorine.

Aryl represents aromatic, mono or polycyclic hydrocarbon rings, such as,for example, phenyl, naphthyl, anthranyl, phenanthryl, preferably phenylof naphthyl, in particular phenyl.

Heterocyclyl represents saturated or unsaturated, and also aromatic,cyclic compounds in which at least one ring member is a heteroatom, i.e.an atom different from carbon. If the ring contains a plurality ofheteroatoms, these can be identical or different. Preferred heteroatomsare oxygen, nitrogen or sulphur. If appropriate, the cyclic compoundsform a polycyclic ring system together with other carbocyclic orheterocyclic, fused-on or bridged rings. Preference is given to mono- orbicyclic ring systems, in particular to mono- or bicyclic aromatic ringsystems.

Cycloalkyl represents saturated, carbocyclic, cyclic compounds which, ifappropriate, form a polycyclic ring system with other carbocyclic,fused-on or bridged rings.

Furthermore, it has been found that the novel alkoximinomethyldioxazinederivatives of the general formula (I) are obtained when (process a)3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines of the general formula

in which

E¹, E², E³, E⁴, L¹, L², L³ and L⁴ each as defined above, are reactedwith an acrylic acid halide of the general formula (III)

 in which

G, R¹, R² and Z are each as defined above, and

X represents halogen,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor.

Finally, it has been found that the novel alkoximinomethyldioxazinederivatives of the general formula (I) have very strong fungicidalactivity.

The compounds according to the invention may, if appropriate, be presentas mixtures of different possible isomeric forms, in particular ofstereoisomers, such as, for example, 20

E- and Z- or optical isomers. What is claimed are both the E and the Zisomers, the individual enantiomers, the racemates, and also anymixtures of these isomers.

The present application preferably provides alkoximinomethyldioxazinderivatives of the formula (I) in which

R¹ represents hydrogen, cyano or represents alkyl having 1 to 6 carbonatoms which is optionally substituted by halogen or alkoxy having 1 to 4carbon atoms or represents cycloalkyl having 3 to 8 carbon atoms whichis optionally substituted by halogen, alkyl or alkoxy having in eachcase 1 to 4 carbon atoms,

R² represents hydrogen or represents alkyl having 1 to 6 carbon atomswhich is optionally substituted by halogen or alkoxy having 1 to 4carbon atoms or represents cycloalkyl having 3 to 8 carbon atoms whichis optionally substituted by halogen, alkyl or alkoxy having in eachcase 1 to 4 carbon atoms,

G represents a single bond, alkanediyl having 1 to 5 chain members whichis optionally interrupted by one or two heteroatoms (but where thecarbon atom to which R¹ is attached is always linked to a carbon atom ofthe alkanediyl chain) or a grouping

 in which

R³ represents hydrogen or represents alkyl having 1 to 6 carbon atoms,alkenyl having 2 to 6 carbon atoms or alkinyl having 2 to 6 carbonatoms, each of which is optionally substituted by halogen or alkoxyhaving 1 to 4 carbon atoms, or represents cycloalkyl having 3 to 8carbon atoms which is optionally substituted by halogen, alkyl or alkoxyhaving in each case 1 to 4 carbon atoms or represents arylalkyl having 1to 4 carbon atoms in the alkyl moiety, which is optionally substitutedin the aryl moiety, where the substituents are selected from the listbelow:

halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, in each casestraight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms, in each casestraight-chain or branched alkenyl, alkenyloxy or alkinyloxy having ineach case 2 to 6 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkyl-sulphinyl or halogenoalkylsulphonyl having in each case 1to 6 carbon atoms and 1 to 13 identical or different halogen atoms, ineach case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms, in each case straight-chain orbranched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy,alkoxycarbonyl, alkylsulphonyloxy, hydroximinoalkyl or alkoximinoalkylhaving in each case 1 to 6 carbon atoms in the individual alkylmoieties, in each case doubly attached alkylene or dioxyalkylene havingin each case 1 to 6 carbon atoms and being in each case optionally mono-or polysubstituted by identical or different substituents selected fromthe group consisting of halogen and straight or branched halogenoalkylhaving 1 to 4 carbon atoms and 1 to 9 identical or different halogenatoms,

Z represents alkyl having 1 to 8 carbon atoms, which is optionally mono-or polysubstituted by identical or different substituents selected fromthe group consisting of halogen, cyano, hydroxyl, amino, C₁-C₄-alkoxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl and C₁-C₄-alkylsulphonyl (each ofwhich may optionally be substituted by halogen);

represents in each case optionally halogen-substituted alkenyl oralkinyl having in each case up to 8 carbon atoms; or represents phenyl,naphthyl, cycloalkyl or cycloalkenyl having in each case 3 to 8 carbonatoms and being in each case optionally mono- or polysubstituted byidentical or different substituents, or represents heterocyclyl having 3to 7 ring members, at least one of which represents oxygen, sulphur ornitrogen and another one or two of which optionally represent nitrogen,where the possible substituents are preferably selected from the listbelow:

halogen, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl,thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkylthio,alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbonatoms;

in each case straight-chain or branched alkenyl or alkenyloxy having ineach case 2 to 6 carbon atoms;

in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonylhaving in each case 1 to 6 carbon atoms and 1 to 13 identical ordifferent halogen atoms;

in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino,alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkylsulphonyloxy,having in each case 1 to 6 carbon atoms in the individual alkylmoieties.

In each case doubly attached alkylene or dioxyalkylene having in eachcase 1 to 6 carbon atoms and being in each case optionally mono- orpolysubstituted by identical or different substituents selected from thegroup consisting of halogen and, straight-chain or branched alkyl having1 to 4 carbon atoms and straight-chain or branched halogenoalkyl having1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms;

Cycloalkyl having 3 to 8 carbon atoms;

heterocyclyl or heterocyclyl-methyl having in each case 3 to 7 ringmembers, 1 to 3 of which are in each case identical or differentheteroatoms—in particular nitrogen, oxygen and/or sulphur—or a grouping

 in which

A¹ represents alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to6 carbon atoms and

A² represents optionally cyano-, alkoxy-, alkylthio-, alkylamino-,dialkylamino- or phenyl-substituted alkyl having 1 to 4 carbon atoms,alkenyl or alkinyl having in each case 2 to 4 carbon atoms and

E¹, E², E³ and E⁴ are identical or different and, independently of oneanother each represents hydrogen, alkyl or hydroxyalkyl having in eachcase 1 to 4 carbon atoms or halogenoalkyl having 1 to 4 carbon atoms and1 to five identical or different halogen atoms, or

E¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring having five,six or seven carbon atoms and

L¹, L², L³ and L⁴ are identical or different and, independently of oneanother, each represents hydrogen, halogen, cyano, nitro, representsalkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having ineach case 1 to 6 carbon atoms and being in each case optionallysubstituted by 1 to 5 halogen atoms.

The present application relates in particular to compounds of theformula (I) in which

R¹ represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

G represents a single bond, methanediyl, 1,1-ethanediyl, 1,2-ethanediyl,1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-,2,3-butanediyl or 1,1-, 1,2- or 1,3-(2-methyl-propanediyl), —O—CH₂—(where Z is linked to the oxygen atom),

Z

represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of chlorine fluorine,bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl;

represents phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cylohexyl,cycloheptyl, oxazolyl, benzofuranmyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl,pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,1,3,5-triazinyl or 5,6-dihydro-1,4,2-dioxazinyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents, where the possible substituents are preferably selectedfrom the list below:

fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl,

in each case doubly attached methylenedioxy, ethylenedioxy, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping

 where

A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,cyclopropyl or cyclobutyl and

A² represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,allyl, propargyl, but-2-en-1-yl, 2-methyl-prop-1-en-3-yl, cyanomethyl,methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl,dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl,methylaminoethyl or benzyl and

E¹, E², E³ and E⁴ are identical or different and, independently of oneanother, each represents hydrogen, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, or

E¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring having five,six or seven carbon atoms and

L¹, L², L³ and L⁴ are identical or different and, independently of oneanother, each represents hydrogen, fluorine, chlorine, bromine, cyano,nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl.

The present application likewise relates in particular to compounds ofthe formula (I) in which

R¹ represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

G represents a grouping

 in which

R³

represents hydrogen or represents methyl, ethyl, n- or i-propyl, n-,-i-, s- or t-butyl, each of which is optionally mono- to trisubstitutedby fluorine, chlorine, bromine, methoxy, ethoxy, (each of which isoptionally substituted by fluorine and/or chlorine),

represents allyl, crotonyl, 1-methyl-allyl, propargyl or1-methyl-propargyl, each of which is optionally mono- to trisubstitutedby fluorine or chlorine;

represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each ofwhich is optionally mono- to hexasubstituted by fluorine, chlorine,bromine, methoxy, ethoxy, phenyl (which is optionally substituted byfluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy,difluoromethoxy or trifluoromethoxy), methyl, ethyl, n- or i-propyl;

represents benzyl, phenyl-1-ethyl or phenyl-2-ethyl, each of which isoptionally mono- to trisubstituted in the phenyl moiety, where thepossible substituents are preferably selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i- s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl,trifluoromethylsulphonyl, acetyl, propionyl, acetyloxy, methoxycarbonyl,ethoxycarbonyl, methylsulphonyloxy, ethylsulphonyloxy,hydroximinomethyl, hydroximinoethyl, methoximinomethyl,ethoximinomethyl, methoximinoethyl or ethoximinoethyl;

in each case doubly attached trimethylene (propane-1,3-diyl),methylenedioxy or ethylenedioxy, each of which is optionally mono- orpolysubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, methyl, trifluoromethyl, ethyl,n- or i-propyl,

Z

represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of chlorine fluorine,bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorchloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl;

represents vinyl, allyl or propargyl, each of which is optionally mono-to trisubstituted by identical or different substituents selected fromthe group consisting of chlorine fluorine or bromine; or

represents phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, 1,2-oxazolyl, benzofuranyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl,pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,1,3,5-triazinyl or 5,6-dihydro-1,4,2-dioxazinyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents, where the possible substituents are preferably selectedfrom the list below:

fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl,

in each case doubly attached methylenedioxy, ethylenedioxy, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl or ethyl or a grouping

 where

A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,cyclopropyl or cyclobutyl and

A² represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,allyl, propargyl, but-2-en-1-yl, 2-methyl-prop-1-en-3-yl, cyanomethyl,methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl,dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl,methylaminoethyl or benzyl and

E¹, E², E³ and E⁴ are identical or different and, independently of oneanother, each represents hydrogen, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, or

E¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring having five,six or seven carbon atoms and

L¹, L², L³ and L⁴ are identical or different and, independently of oneanother, each represents hydrogen, fluorine, chlorine, bromine, cyano,nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl.

A particularly preferred group of compounds according to the inventionare the compounds of the formula (I) in which

R¹ represents cyclopropyl or, in particular, methyl,

R² represents hydrogen,

G represents a single bond or —O—CH₂— (where Z is attached to the oxygenatom),

Z

represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each ofwhich is optionally mono- to trisubstituted by identical or differentconstituents selected from the group consisting of chlorine fluorine,bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl andtrifluoromethylsulphonyl; or

represents 1,2-oxazolyl, benzofuranyl or phenyl which is optionallymono- to trisubstituted by identical or different substituents, wherethe possible substituents are preferably selected from the list below:

fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, or represents

in each case doubly attached methylenedioxy, ethylenedioxy, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping

 where

A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,cyclopropyl or cyclobutyl and

A² represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,allyl, propargyl, but-2-en-1-yl, 2-methyl-prop-1-en-3-yl, cyanomethyl,methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl,dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl,methylaminoethyl or benzyl,

E¹ and E² are identical or different and, independently of one another,each represents methyl, or in particular, hydrogen,

E³ and E⁴ each represents hydrogen,

L¹ and L³ are identical or different and, independently of one another,each represents methyl, or in particular, hydrogen and

L² and L⁴ each represents hydrogen.

Another particularly preferred group of compounds according to theinvention are those compounds of the formula (I) in which

R¹ represents cyclopropyl or, in particular, methyl,

R² represents hydrogen,

G represents a grouping

 in which

R³ represents methyl or represents benzyl which is optionally mono- totrisubstituted in the phenyl moiety by fluorine, chlorine, bromine,cyano, nitro, methyl or methoxy,

Z

represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,trifluoromethyl, trifluorethyl, methoxymethyl, methylthiomethyl ormethylsulphonylmethyl, vinyl, dichlorovinyl, allyl, propargyl,cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cylohexyl or

represents 1,2-oxazolyl, benzofuranyl or, in particular, phenyl each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents, where the possible substituents are preferably selectedfrom the list below:

fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorchloromethoxy, trifluorethoxy,difluoromethylthio, trifluoromethylthio, difluorochloromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, methoxycarbonyl,ethoxycarbonyl; or represents

in each case doubly attached methylenedioxy, ethylenedioxy, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping

 where

A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,cyclopropyl or cyclobutyl and

A² represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,allyl, propargyl, but-2-en-1-yl, 2-methyl-prop-1-en-3-yl, cyanomethyl,methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl,methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl,dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl,methylaminoethyl or benzyl,

E¹ and E² are identical or different and, independently of one another,each represents methyl, or in particular, hydrogen,

E³ and E⁴ each represents hydrogen,

L¹ and L³ are identical or different and, independently of one another,each represents methyl, or in particular, hydrogen and

L² and L⁴ each represents hydrogen.

The abovementioned general or preferred radical definitions apply bothto the end products of the formula (I) and, correspondingly, to thestarting materials or intermediates required in each case for thepreparation.

Independently of the combination given in each case, the definitions ofradicals given in the combinations or preferred combinations of radicalsin question specifically for these radicals are also replaced at will bydefinitions of radicals of the other preferred ranges in question.

The formula (II) provides a general definition of the3-(1-hydroxyphenyl-1-alkoxirninomethyl)dioxazines required as startingmaterials for carrying out the process a) according to the invention. Inthis formula (II), E¹, E², E³, E⁴, L¹, L², L³ and L⁴ each preferably orin particular have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred or as being particularlypreferred for E¹, E², E³, E⁴, L¹, L², L³ and L⁴.

The 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines of the formula (II)are known and can be prepared by known processes (WO 95-04728).

The formula (III) provides a general definition of the acrylic acidhalides furthermore required as starting materials for carrying out theprocess a) according to the invention. In this formula (III) G, R¹, R²and Z each preferably or in particular have those meanings which havealready been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingpreferred or as being particularly preferred for G, R¹, R² and Z. Xrepresents halogen, preferably chlorine.

Some of the acrylic acid halides of the formula (III) are known(Balsamo, A.; Crotti, P.; Lapucci, A.; Macchia, B.; Macchia, F.; et al.,J.Med.Chem., 24, 5, 1981, 525-532) and/or they can be prepared byprocesses known per se from the corresponding acrylic acids (compare,for example, Padmanathan,T.; Sultanbawa, M. U. S., J.Chem.Soc., 1963,4210-4218 or Wiley; van der Plas, J.Chem.Eng.Data, 10, 1965, 72) byhalogenation with customary halogenating agents, such as, for example,thionyl chloride or oxalyl chloride.

Novel, and also part of the subject matter of the present application,are acrylic acid halides of the general formula (III-a)

in which

R¹, R², R³, X and Z are each as defined above.

The acrylic acid halides of the formula (III-a) are obtained when(process b) acrylic acids of the general formula (IV)

in which

R¹, R², R³ and Z are each as defined above

are reacted with an halogenating agent, such as, for example, thionylchloride, phosgene, phosphorus pentachloride or phosphorus oxychloride,if appropriate in the presence of a diluent, such as, for example,1,2-dichloroethane, at temperatures of from 0 to 150° C. (compare alsothe preparation examples).

The formula (IV) provides a general definition of the acrylic acidsrequired as starting materials for carrying out the process b) accordingto the invention. In this formula (IV), R¹, R², R³ and Z each preferablyor in particular have those meanings which have already been mentionedin connection with the description of the compounds of the formula (I)according to the invention as being preferred or as being particularlypreferred for R¹, R², R³ and Z.

As novel substances, the acrylic acids of the formula (IV) also formpart of the subject matter of the present application. They are obtainedwhen (process c) acrylic esters of the formula (V)

in which

R¹, R², R³ and Z are each as defined above and

R⁴ represents alkyl

are hydrolyzed, if appropriate in the presence of a diluent, for examplean alcohol, such as methanol or ethanol, if appropriate in the mixturewith water, and if appropriate in the presence of a base, such as, forexample, sodium hydroxide or potassium hydroxide, or an acid, such as,for example, hydrochloric acid or sulphuric acid.

The formula (V) provides a general definition of the acrylic estersrequired as starting materials for carrying out the process c) accordingto the invention. In this formula (V), R¹, R², R³ and Z each preferablyor in particular have those meanings which have already been mentionedin connection with the description of the compounds of the formula (I)according to the invention as being preferred or as being particularlypreferred for R¹, R², R³ and Z. R⁴ represents alkyl, preferably methylor ethyl.

As novel substances, the acrylic esters of the formula (V) also formpart of the subject matter of the present application. They are obtainedwhen (process d) α-diketone monooximes of the formula (VI)

in which

R¹, R³ and Z are each as defined above

are reacted with a dialkyl alkoxycarbonylmethanephosphonate of theformula (VII)

in which

R² and R⁴ are each as defined above and

R⁵ represents alkyl,

if appropriate in the presence of a diluent, for example an ether, suchas tetrahydrofuran, and if appropriate in the presence of a base, suchas, for example, potassium t-butoxide or sodium hydride.

The formula (VI) provides a general definition of the α-diketonemonooximes required as starting materials for carrying out the processd) according to the invention. In this formula (VI), R¹, R³ and Z eachpreferably or in particular have those meanings which have already beenmentioned in connection with the description of the compounds of theformula (I) according to the invention as being preferred or as beingparticularly preferred for R¹, R³ and Z.

The α-diketone monooximes of the formula (VI) are known and/or can beprepared by known methods (compare, for example, Diels; Stern,Chem.Ber., 40 (1907),1624).

The formula (VII) provides a general definition of the dialkylalkoxycarbonylmethanephosphonate furthermore required as startingmaterials for carrying out the process d) according to the invention. Inthis formula (VII), R² and R⁴ each preferably or in particular havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred or particularly preferred for R² and R⁴. R⁵represents alkyl, preferably methyl or ethyl. The dialkylalkoxycarbonylmethanephosphonates of the formula (VII) are knownchemicals for synthesis.

Suitable diluents for carrying out the process a) according to theinvention are all inert organic solvents. These preferably includealiphatic, alicyclic or aromatic hydrocarbons, such as, for example,petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane,benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as,for example, chlorobenzene, dichlorobenzene, dichloromethane,chloroform, carbon tetrachloride, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- dimethoxyethane,1,2-diethoxyethane or anisol; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; Esters such as methyl acetate or ethylacetate; sulphones, such as sulpholane, and also amines, such aspyridine.

The process a) according to the invention is, if appropriate, carriedout in the presence of a suitable acid acceptor. Suitable acid acceptorsare all customary inorganic or organic bases. These preferably includealkaline earth metal or alkali metal hydrides, hydroxides, amides,alkoxides, acetates, carbonates or bicarbonates, such as, for example,sodium hydride, sodium amide, sodium methoxide, sodium ethoxide,potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammoniumhydroxide, sodium acetate, potassium acetate, calcium acetate, ammoniumacetate, sodium carbonate, potassium carbonate, potassium bicarbonate,sodium bicarbonate or ammonium carbonate, and also tertiary amines, suchas trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, N-methylpiperidine,N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane(DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out the process a) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures from 0° C. to 150°C., preferably at temperatures from 0° C. to 80° C.

When carrying out the process a) according to the invention forpreparing the compounds of the formula (I), generally from 1 to 15 mol,preferably from 1 to 8 mol, of an acrylic acid halide of the formula(III) are employed per mole of3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazine of the formula (II).

The processes according to the invention are generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure—in general between 0.1 bar and 10 bar.

The compounds according to the invention have a potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides are employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides are employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above are mentioned as examples, but not in alimiting way:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae,

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochiobolus sativus (conidiaform: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of aerial parts of plants, of propagation stock and seeds, andof the soil.

The active compounds according to the invention can be employedparticularly successfully for controlling cereal diseases, such as, forexample, against Leptosphaeria species, for controlling diseases inviticulture and fruit and vegetable growing, such as, for example,against Venturia and Plasmopara species. or for controlling ricediseases, such as, for example, against Pyricularia species. Othercereal diseases, such as, for example, Septoria, Pyrenophora orCochliobolus species, are controlled very successfully.

Furthermore, the compounds according to the invention may also beemployed to increase the yield of crops. Moreover, they exhibit reducedtoxicity and are tolerated well by plants.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to employ,for example, organic solvents as auxiliary solvents. Essentially, thefollowing are suitable for use as liquid solvents: aromatics such asxylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water. Liquefied, gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at standardtemperature and under atmospheric pressure, for example aerosolpropellants such as halogenated hydrocarbons, or else butane, propane,nitrogen and carbon dioxide. Suitable solid carriers are: for exampleground natural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals such as highly disperse silica, alumina and silicates. Suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,or else synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks. Suitable emulsifiers and/or foam formers are: forexample nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates. Suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

The active compounds according to the invention can be used as such orin their formulations also mixed with known fungicides, bactericides,acaricides, nematicides or insecticides in order thus, for example, towiden the spectrum of action or to prevent development of resistance. Inmany cases, synergistic effects are achieved, i.e. the activity of themixture exceeds the activity of the individual components.

Examples of co-components in mixtures are the following compounds:

Fungicides

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone-O-(phenylmethyl)-oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidindione,

1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrol-2,5-dione,

3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethylmorpholinehydrochloride,

ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulfonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,

N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin,

Bacillus thuringiensis,4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethanimidamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth-promoting substances.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bypouring, spraying, atomizing, spreading, dusting, foaming, brushing onand the like. It is further possible to apply the active compounds bythe ultra-low volume method or to inject the active compoundformulation, or the active compound itself, into the soil. The seed ofthe plants can also be treated.

When the active compounds according to the invention are employed asfungicides, the application rates can be varied within a relatively widerange, depending on the type of application. For the treatment of partsof plants, the active compound application rates are generally between0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. For thetreatment of seeds, the active compound application rates are generallybetween 0.001 and 50 g per kilogram of seeds, preferably between 0.01and 10 g per kilogram of seeds. For the treatment of the soil, theactive compound application rates are generally between 0.1 and 10,000g/ha, preferably between 1 and 5000 g/ha.

PREPARATION EXAMPLES EXAMPLE 1

Process a)

0.69 g (0.003 mol) of 3-(3-trifluoromethyl-phenyl)-but-2-enoic acid,0.39 g (0.0033 mol) of thionyl chloride and 10 ml of 1,2-dichloroethaneare boiled under reflux for one hour. Volatile components are distilledoff under reduced pressure and the residue, the crude3-(3-trifluoromethyl-phenyl)-but-2-enoyl chloride, is dissolved in 20 mlof dimethylformamide. This solution is added dropwise to a mixture of0.62 g (0.0027 mol) of(5,6-dihydro-[1,4,2]dioxazin-3-yl)-(2-hydroxy-phenyl)-methanoneO-methyl-oxime and 0.848 g (0.0028 mol) of an 80% strength sodiumhydride suspension in 30 ml of dimethylformamide, and stirring iscontinued for another 16 hours. The reaction mixture is then poured into50 ml of water and extracted twice with 50 ml of ethyl acetate eachtime, the organic phase is dried over sodium sulphate and the solvent isdistilled off under reduced pressure. The residue is chromatographedover silica gel using ethyl acetate/cyclohexane (1:1). This gives 0.99 g(82% of theory) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyiminomethyl]-phenyl3-(3-trifluoromethylphenyl)-but-2-enoate.

¹H-NMR-Spectrum (CDCl₃/TMS): δ=2.64 (s, 3H); 3.94 (s, 3H); 4.17 (m, 2H);4.48 (m, 2H); 6.34 (s, 1H); 7.26-7.78 (m, 8H) ppm.

Preparation of the Starting Material

34 g (0.139 mol) of methyl 3-(3-trifluoromethyl-phenyl)-but-2-enoate aredissolved in 200 ml of methanol, admixed with 24.8 g (0.28 mol) of 45%strength aqueous sodium hydroxide solution and stirred at 20° C. for 16hours. The solvent is distilled off under reduced pressure and theresidue is taken up in 100 ml of water, acidified using approximately150 ml of 2N hydrochloric acid (pH≈1) and extracted twice with 50 ml ofethyl acetate each time. The organic phase is dried over sodiumsulphate, the solvent is distilled off under reduced pressure and theresidue is stirred with petroleum ether. This gives 17 g (53% of theory)of 3-(3-trifluoromethyl-phenyl)-but-2-enoic acid.

¹H-NMR spectrum (CDCl₃/TMS): δ=2.62 (d, 3H); 6.19 (q, 1H); 7.48-7.55(1H); 7.64-7.73 (3H) ppm.

Preparation of the Precursor

At 0° C., 33.2 g (0.183 mol) of dimethylmethoxycarbonylmethanephosphonate are added dropwise to a solution of20.5 g (0.183 mol) of potassium tert-butoxide in 200 ml oftetrahydrofuran. At 20° C., 31.2 g (0.166 mol) of3-(trifluoromethyl)-acetophenone are added dropwise, and the mixture issubsequently boiled under reflux for three hours. The solvent isdistilled off under reduced pressure, and the residues are mixed with200 ml of water and extracted twice with 100 ml of ethyl acetate eachtime. The organic phase is dried over sodium sulphate and the solvent isdistilled off under reduced pressure. The product is then distilled at0.5 torr and 80-90° C. This gives 34.6 g (85.4% of theory) of methyl3-(3-trifluoromethyl-phenyl)-but-2-enoate as a mixture of stereoisomers.

¹H-NMR-spectrum (CDCl₃/TMS): δ=2.20 (d, 3H, Z isomer); 2.59 (d, 3H, Eisomer); 3.56 (3H, Z isomer); 3.77 (3H, E isomer); 5.98 (q, 1H, Zisomer); 6.16 (q, 1H, E isomer); 7.27-8.22 (4H) ppm.

EXAMPLE 2

Process a)

180 mg (0.0045 mol) of a 60% strength sodium hydride suspension areadded to a solution of 1.08 g (0.0046 mol) of(5,6-dihydro-[1,4,2]dioxazin-3-yl)-(2-hydroxy-phenyl)-methanoneO-methyl-oxime in 5 ml of dimethylformamide, and the mixture is stirreduntil evolution of gas ceases. At 0° C., 0.8 g (0.0045 mol) of4-methoxyimino-3-methyl-pent-2-enoic chloride is added dropwise. Thereaction mixture is allowed to stand for 10 minutes and poured intowater, and the mixture is extracted with 10 ml of ethyl acetate. Theorganic phase is dried over sodium sulphate and the volatile componentsare distilled off under reduced pressure. The residue is stirred withpetroleum ether. This gives 2.09 g (32.6% of theory) of2-[(5,6-dihydro-[1,4,2]dioxazin-3-yl)-methoxyiminomethyl]-phenyl ester4-methoxyimino-3-methylpent-2-enoate as oil.

¹H-NMR spectrum (CDCl₃/TMS): δ=2.03 (3H); 2.41 (d, 3H); 3.92 (3H); 4.00(3H); 4.09-4.17 (2H); 4.45-4.48 (2H); 6.24 (q, 1H), 7.25-7.32 (3H); ppm.

Preparation of the Starting Material

EXAMPLE (III-a-1)

Process b)

1.6 g (0.01 mol) of 4-methoxyimino-3-methylpent-2-enoic acid and 1.8 g(0.015 mol) of thionyl chloride in 10 ml of dichloroethane are heatedunder reflux for 30 minutes. Volatile components are distilled off underreduced pressure and the residue is distilled under high vacuum. Thisgives 0.8 g (45% of theory) of 4-methoxyimino-3-methylpent-2-enoicchloride as a mixture of stereoisomers.

¹H-NMR spectrum (CDCl₃/TMS): δ=2.00 (3H, isomer A+isomer B); 2.11/2.12(d, 3H, isomer B); 2.33/2.33 (d, 3H, isomer A); 3,92 (3H, isomer B);4.02 (3H, isomer A); 5.88 (1H, isomer B); 6.36/6.37 (q, 1H, isomer A)ppm.

Preparation of the Precursor

EXAMPLE (IV-1)

Process c)

35.8 g (0.209 mol) of methyl 4-methoxyimino-3-methylpent-2-enoate aredissolved in 600 ml of methanol, admixed with 300 ml of 2N sodiumhydroxide solution and boiled under reflux for 30 minutes. The solventis distilled off under reduced pressure and the residue is taken up in300 ml of water and acidified with approximately 350 ml of 2Nhydrochloric acid (pH≈1). The product precipitates out and is filteredoff. This gives 18.2 g (55.4% of theory) of4-methoxyimino-3-methylpent-2-enoic acid as the mixture of thestereoisomers.

¹H-NMR spectrum (CDCl₃/TMS): δ=2.00 (s, 3H, isomer A); 2.01 (s, 3H,isomer B); 2.06/2.07 (d, 3H, isomer B); 2,37 (d, 3H, isomer A); 3.90 (s,3H, isomer B); 3.99 (s, 3H, isomer A); 5.59 (1H, isomer B); 6.10 (q, 1H,isomer A) ppm.

Preparation of the Precursor

EXAMPLE (V-1)

Process d)

At 0° C., 12.4 g (0.068 mol) of dimethylmethoxycarbonylmethanephosphonate are added dropwise to a solution of7.63 g (0.068 mol) of potassium tert-butoxide in 70 ml oftetrahydrofuran. At 20° C., 7.83 g (0.068 mol) of butane-2,3-dionemono-(O-methyl-oxime) are then added dropwise, and the mixture issubsequently boiled under reflux for 30 minutes. The solvent isdistilled off under reduced pressure and the residue is mixed with 50 mlof water and extracted twice with 50 ml of diethyl ether each time. Theorganic phase is dried over sodium sulphate and the solvent is distilledoff under reduced pressure. The product is then distilled at 17 torr.This gives 5.16 g (44% of theory) of methyl4-methoxyimino-3-methylpent-2-enoate as a mixture of stereoisomers witha boiling range of from 95 to 105° C.

¹H-NMR spectrum (CDCl₃/TMS): δ=1.98 (s, 3H, isomer A); 2.00 (s, 3H,isomer B); 2.03 (d, 3H, isomer B); 2.35 (d, 3H, isomer A); 3.69 (s, 3H,isomer B); 3.74 (s, 3H, isomer A); 3.89 (s, 3H, isomer B); 3.98 (s, 3H,isomer A); 5.83 (q, 1H, isomer B); 6.08 (q, 1H, isomer A) ppm.

The compounds of the formula (I-a) according to the invention listed inTable 1 below are also obtained by the methods of Examples (1) and (2),and in accordance with the general description of the preparationprocess a) according to the invention:

TABLE 1 Ex. No. Z G E¹ E² L¹ L³ phys. data 3 3- —O—CH₂— —H —H —H —Htrifluoromethylphenyl 4 3-bromophenyl — —H —H —H —H logP: 3.72 53-methoxyphenyl — —H —H —H —H logP: 3.22 6 phenyl — —H —H —H —H logP:3.22 7 4-trifluoromethyl — —H —H —H —H logP: 3.81 8 4-tolyl — —H —H —H—H logP: 3.58 9 3-ethylphenyl — —H —H —H —H logP: 3.91 10 4-bromophenyl— —H —H —H —H logP: 3.78 12 4-ethoxyphenyl — —H —H —H —H logP: 3.57 134-tolyl — —H —H —H —H logP: 4.06 14 2,5-dichlorophenyl — —H —H —H —HlogP: 3.93 15 4-chlorophenyl — —H —H —H —H 16 3,4-dichlorophenyl — —H —H—H —H 17 3-tolyl — —H —H —H —H logP: 3.58 18 3,4-dimethoxyphenyl — —H —H—H —H 19 3-chlorophenyl — —H —H —H —H logP: 3.64 20 4-fluorophenyl — —H—H —H —H logP: 3.28 21 4-methoxyphenyl — —H —H —H —H logP: 3.19 224-trifluoromethyl — —CH₃ —H —H —H logP: 4.02 23 4-trifluoromethyl — —CH₃—CH₃ —H —H logP: 4.23 24 2-(i-propoxy)phenyl — —H —H —H —H logP: 3.87 252-ethoxyphenyl — —H —H —H —H logP: 3.63 26 2-propoxyphenyl — —H —H —H —HlogP: 3.98 27

— —H —H —H —H 28 2-chlorophenyl — —H —H —H —H 29 2-fluorophenyl — —H —H—H —H logP: 3.25 30 4-methoxyphenyl —O—CH₂— —H —H —H —H 31 4-tolyl—O—CH₂— —H —H —H —H 32 3-chlorophenyl — —H —H —H —CH₃ logP: 3.90 33phenyl

—H —H —H —H 34 4-fluorophenyl

—H —H —H —H 35 4-chlorophenyl

—H —H —H —H 36 3-chlorophenyl

—H —H —H —H 37 4-tolyl

—H —H —H —H 38 4-cyanophenyl

—H —H —H —H 39 3-cyanophenyl

—H —H —H —H 40

—H —H —H —H 41 i-propyl

—H —H —H —H 42 2-methoxyphenyl — —H —H —H —H logP: 3.28 432-trifluorophenyl — —H —H —H —H logP: 3.58 44 2,5-dimethylphenyl — —H —H—H —H logP: 3.85 45 2-bromophenyl — —H —H —H —H logP: 3.58 46

— —H —H —H —H logP: 2.75 47 2-methylphenyl — —H —H —H —H logp: 3.48

Use Examples

EXAMPLE A

Plasmopara Test (Grapevine)/Protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, the young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at approximately 20° C. and 100% relative atmospheric humidity for1 day. The plants are subsequently placed in a greenhouse atapproximately 21° C. and approximately 90% relative atmospheric humidityfor 5 days. The plants are then moistened and placed in an incubationcabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds of PreparationExamples (1), (4), (5), (6), (8) and (9) exhibit, at an exemplary activecompound application rate of 100 g/ha, an efficacy of up to 100% incomparison with the untreated control.

EXAMPLE B

Venturia Test (Apple)/Protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousconidia suspension of the causative organism of apple scab Venturiainaequalis and then remain in an incubation cabin at approximately 20°C. 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approximately 21° C. anda relative atmospheric humidity of approximately 90%.

Evaluation is carried out 12 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds of PreparationExamples (1), (4), (5), (6), (7), (8) and (9) exhibit, at an exemplaryactive compound application rate of 10 g/ha, an efficacy of up to 100%in comparison with the untreated controls.

EXAMPLE C

Leptosphaeria Nodorum Test (Wheat)/Protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a sporesuspension of Leptosphaeria nodorum. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of approximately15° C. and a relative atmospheric humidity of 80%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compound of the PreparationExamples (4) exhibits, at an exemplary active compound application rateof 25 g/ha, an efficacy of 70% in comparison with the untreated control.

EXAMPLE D

Pyricularia Test (Rice)/Protective

Solvent: 2.5 parts by weight of acetone

Emulsifier: 0.06 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and theconcentrate is diluted with water and the stated amount of emulsifier tothe diluted concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation is carried out 4 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds of the PreparationExamples (3), (7), (8) and (9) exhibit, at an exemplary active compoundapplication rate of 750 g/ha and a contact time of one day, an efficacyof more than 80% in comparison with the untreated control.

EXAMPLE E

Puccinia Test (Wheat)/Protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.06 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at temperature ofapproximately 20° C. and a relative atmospheric humidity of 80% topromote the development of crude pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

What is claimed is:
 1. Compounds of the formula (I)

in which R¹ represents hydrogen, cyano or represents alkyl having 1 to 6carbon atoms which is optionally substituted by halogen or alkoxy having1 to 4 carbon atoms or represents cycloalkyl having 3 to 8 carbon atomswhich is optionally substituted by halogen, alkyl or alkoxy having ineach case 1 to 4 carbon atoms, R² represents hydrogen or representsalkyl having 1 to 6 carbon atoms which is optionally substituted byhalogen or alkoxy having 1 to 4 carbon atoms or represents cycloalkylhaving 3 to 8 carbon atoms which is optionally substituted by halogen,alkyl or alkoxy having in each case 1 to 4 carbon atoms, G represents asingle bond, methanediyl, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-, 1,2-,1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2,3-butanediyl or1,1-, 1,2- or 1,3-(2-methyl-propanediyl), —O—CH₂— (where Z is attachedto the oxygen atom), Z represents methyl, ethyl, n- or i-propyl, n-, i-,s- or t-butyl, each of which is optionally mono- to trisubstituted byidentical or different substituents selected from the group consistingof chlorine fluorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethyl-sulphinylor trifluoromethylsulphonyl; represents phenyl, cyclopropyl, cyclobutyl,cyclopentyl, cylohexyl, cycloheptyl, oxazolyl, benzofuranyl,1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl,1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or5,6-dihydro-1,4,2-dioxazinyl, each of which is optionally mono- totrisubstituted by identical or different substituents, where thepossible substituents are preferably selected from the list below:fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methoxy-carbonyl, ethoxycarbonyl, in each casedoubly attached methylenedioxy, ethylenedioxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping,

 where A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, cyclopropyl or cyclobutyl and A² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl,2-methyl-prop-1-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, dimethylaminomethyl,dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl andE¹, E², E³ and E⁴ are identical or different and, independently of oneanother each represents hydrogen, alkyl or hydroxyalkyl having in eachcase 1 to 4 carbon atoms or halogenoalkyl having 1 to 4 carbon atoms and1 to five identical or different halogen atoms, or E¹ and E² or E¹ andE³ or E³ and E⁴ together with the respective carbon atoms to which theyare attached form a cycloaliphatic ring having five, six or seven carbonatoms and L¹, L², L³ and L⁴ are identical or different and,independently of one another, each represents hydrogen, halogen, cyano,nitro, represents alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms and being in eachcase optionally substituted by 1 to 5 halogen atoms.
 2. Compounds of theformula (I) according to claim 1 in which R¹ represents hydrogen, cyano,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl,trifluoroethyl, cyclopropyl, cyclobutyl, R² represents hydrogen, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl,trifluoroethyl, cyclopropyl, cyclobutyl, G represents a single bond,methanediyl, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-, 1,2-, 1,3- or2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2,3-butanediyl or 1,1-,1,2- or 1,3-(2-methyl-propanediyl), —O—CH₂— (where Z is attached to theoxygen atom), Z represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, each of which is optionally mono- to trisubstituted byidentical or different substituents selected from the group consistingof chlorine fluorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl,ethylsulphonyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl; represents phenyl, cyclopropyl, cyclobutyl,cyclopentyl, cylohexyl, cycloheptyl, oxazolyl, benzofuranyl,1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl,1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or5,6-dihydro-1,4,2-dioxazinyl, each of which is optionally mono- totrisubstituted by identical or different substituents, where thepossible substituents are preferably selected from the list below:fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, in each casedoubly attached methylenedioxy, ethylenedioxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping

 where A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, cyclopropyl or cyclobutyl and A² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl,2-methyl-prop-1-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, dimethylaminomethyl,dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl andE¹, E², E³ and E⁴ are identical or different and, independently of oneanother, each represents hydrogen, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, orE¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring having five,six or seven carbon atoms and L¹, L², L³ and L⁴ are identical ordifferent and, independently of one another, each represents hydrogen,fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonylor ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl.
 3. Compounds ofthe formula (I) according to claim 1, in which R¹ represents methyl orcyclopropyl, R² represents hydrogen, G represents a single bond or—O—CH₂— (where Z is attached to the oxygen atom), Z represents methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which isoptionally mono- to trisubstituted by identical or differentconstituents selected from the group consisting of chlorine fluorine,bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl andtrifluoromethylsulphonyl; represents phenyl, 1,2-oxazolyl orbenzofuranyl which is optionally mono- to trisubstituted by identical ordifferent substituents, where the possible substituents are preferablyselected from the list below: fluorine, chlorine, bromine, cyano,methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy,n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, in eachcase doubly attached methylenedioxy, ethylenedioxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping,

 where A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, cyclopropyl or cyclobutyl and A² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl,2-methyl-prop-1-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, dimethylaminomethyl,dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl, E¹and E² are identical or different and, independently of one another,each represents hydrogen or methyl, E³ and E⁴ each represent hydrogen,L¹ and L³ are identical or different and, independently of one another,each represents hydrogen or methyl and L² and L⁴ each representhydrogen.
 4. A pesticide composition comprising at least one compound ofthe formula (I) according to claim 1 and an extender and/or surfactant.5. A method for controlling pests comprising applying compounds of theformula (I) according to claim 1 on pests and/or their habitat.
 6. Aprocess for preparing compounds of the formula (I) as defined in claim 1comprising reacting 3-(1-hydroxy-phenyl-1-alkoximinomethyl)dioxazines ofthe general formula

wherein E¹, E², E³, E⁴, L¹, L², L³, and L⁴ are each as defined in claim2 with an acrylic acid halide of the general formula (III)

 wherein G, R¹, R² and Z are each as defined in claim 2 and X representsa halogen.
 7. The process of claim 6 wherein the reaction is carried outin the presence of a diluent and/or an acid acceptor.
 8. Compoundsaccording to claim 1, wherein E¹, E², E³ and E⁴ are identical ordifferent and, independently of one another each represents hydrogen,alkyl or hydroxyalkyl having in each case 1 to 4 carbon atoms orhalogenoalkyl having 1 to 4 carbon atoms and 1 to five identical ordifferent halogen atoms.
 9. Compounds according to claim 1, wherein L¹,L², L³ and L⁴ are identical or different and, independently of oneanother, each represents hydrogen or halogen, or represents alkyl oralkoxy having in each case 1 to 6 carbon atoms and being in each caseoptionally substituted by 1 to 5 halogen atoms.
 10. Compounds of theformula (I)

in which R¹ represents hydrogen, cyano, methyl, ethyl, n- or i-propyl,n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl,cyclobutyl, R² represents hydrogen, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl,cyclobutyl, G represents a grouping

 in which R³ represents hydrogen or represents methyl, ethyl, n- ori-propyl, n-, -1-, s- or t-butyl, each of which is optionally mono- totrisubstituted by fluorine, chlorine, bromine, methoxy, ethoxy, (each ofwhich is optionally substituted by fluorine and/or chlorine), representsallyl, crotonyl, 1 -methyl-allyl, propargyl or 1 -methyl-propargyl, eachof which is optionally mono- to trisubstituted by fluorine or chlorine;represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each ofwhich is optionally mono- to hexasubstituted by fluorine, chlorine,bromine, methoxy, ethoxy, phenyl (which is optionally substituted byfluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy,difluoromethoxy or trifluoromethoxy), methyl, ethyl, n- or i-propyl;represents benzyl, phenyl-1-ethyl or phenyl-2-ethyl, each of which isoptionally mono- to trisubstituted in the phenyl moiety, where thepossible substituents are preferably selected from the list below:Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i- s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorohloromethoxy,trifluoroethoxy, difluoromethylthio, difluorochloromethylthio,trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl,acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl,methylsulphonyloxy, ethylsulphonyloxy, hydroximinomethyl,hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethylor ethoximinoethyl; in each case doubly attached trimethylene(propane-1,3-diyl), methylenedioxy or ethylenedioxy, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl, ethyl, n- or i-propyl, Z represents methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of chlorine fluorine,bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorchloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl; represents vinyl, allyl or propargyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of chlorine fluorine orbromine; or represents phenyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, 1,2-oxazolyl, benzofuranyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl,pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,1,3,5-triazinyl or 5,6-dihydro-1,4,2-dioxazinyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents, where the possible substituents are preferably selectedfrom the list below: fluorine, chlorine, bromine, cyano, methyl, ethyl,n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl,trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, in eachcase doubly attached methylenedioxy, ethylenedioxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl or ethyl or a grouping

 where A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, cyclopropyl or cyclobutyl and A² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl,2-methyl-prop-1-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, dimethylaminomethyl,dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl andE¹, E², E³ and E⁴ are identical or different and, independently of oneanother, each represents hydrogen, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, orE¹ and E² or E¹ and E³ or E³ and E⁴ together with the respective carbonatoms to which they are attached form a cycloaliphatic ring having five,six or seven carbon atoms and L¹, L², L³ and L⁴ are identical ordifferent and, independently of one another, each represents hydrogen,fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonylor ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl.
 11. Compounds ofthe formula (I)

in which R¹ represents methyl or cyclopropyl, R² represents hydrogen, Grepresents a grouping

 in which R³ represents methyl or represents benzyl which is optionallymono- to trisubstituted in the phenyl moiety by fluorine, chlorine,bromine, cyano, nitro, methyl or methoxy, Z represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl,methoxymethyl, methylthiomethyl or methylsulphonylmethyl, vinyl,dichlorovinyl, allyl, propargyl, cyclopropyl, methylcyclopropyl,cyclobutyl, cyclopentyl, cylohexyl or represents 1,2-oxazolyl,benzofuranyl or, in particular, phenyl each of which is optionally mono-to trisubstituted by identical or different substituents, where thepossible substituents are preferably selected from the list below:fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-,i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio,ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethyisulphinyl ortrifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, in each casedoubly attached methylenedioxy, ethylenedioxy, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,methyl, trifluoromethyl and ethyl or a grouping,

 where A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, cyclopropyl or cyclobutyl and A² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl,2-methyl-prop-1-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl,methylthioethyl, ethylthioethyl, dimethylaminomethyl,dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl, E¹and E² are identical or different and, independently of one another,each represents hydrogen or methyl, E³ and E⁴ each represent hydrogen,L¹ and L³ are identical or different and, independently of one another,each represents hydrogen or methyl and L² and L⁴ each representhydrogen.
 12. A pesticide composition comprising at least one compoundof the formula (I) according to claim 11 and an extender and/orsurfactant.
 13. A method for controlling pests comprising applyingcompounds of the formula (I) according to claim 11 on pests and/or theirhabitat.
 14. A process for preparing compounds of the formula (I) asdefined in claim 11 comprising reacting3-(1-hydroxy-phenyl-1-alkoximinomethyl)dioxazines of the general formula

wherein E¹, E², E³, E⁴, L¹, L², L³, and L⁴ are each as defined in claim6 with an acrylic acid halide of the general formula (III)

 wherein G, R¹, R² and Z are each as defined in claim 11 and Xrepresents a halogen.
 15. The process of claim 14 wherein the reactionis carried out in the presence of a diluent and/or an acid acceptor.